The use of metal-free sulfo group free basic disazo compounds containing two identical 6-hydroxypyrid-2-one coupling component radicals for producing colored paper

ABSTRACT

Metal-free compounds of the formula ##STR1## and 1:1 and 1:2 metal complexes thereof and acid addition salts of such metal-free compounds and 1:1 and 1:2 metal complexes, 
     wherein 
     each B is --A 1  --NR 7  R 8  or --A 1  --.sup.⊕ NR 7  R 8  R 9  A.sup.⊖, the two B&#39;s being identical, 
     wherein 
     each A 1  is linear or branched C 2-8  alkylene, 
     each R 1  is hydrogen, C 1-4  alkyl, C 5-6  cycloalkyl, phenyl, benzyl or phenylethyl, the two R 1  &#39;s being identical, 
     each R 2  is independently halo, hydroxy, nitro, carboxy, C 1-4  alkyl or C 1-4  alkoxy, 
     each T is hydrogen, cyano, --COOR 4 , --CON(R 5 ) 2 , --SO 2  N(R 5 ) 2 , 
     the two T&#39;s being identical, ##STR2## wherein each R 3  is independently hydrogen, C 1-4  alkyl, --N(R 5 ) 2  or --CON(R 5 ) 2 , 
     each R 4  is C 1-6  alkyl or phenyl(C 1-3  alkyl), 
     each R 6  is C 1-4  alkyl, and 
     each X a  is --O--, --S-- or --NR 5  --, and 
     X o  is a direct bond or an organic bridging radical, 
     wherein 
     each R 5  is independently hydrogen or C 1-4  alkyl, or --N(R 5 ) 2  is an unsubstituted saturated ring containing 1 to 3 hetero atoms or a saturated ring containing 1 to 3 hetero atoms and substituted by 1 to 3 C 1-4  alkyl groups, 
     each A.sup.⊖ is a non-chromophoric anion, and R 7  -R 9  are organic radicals, are useful as dye for paper, textiles and leather.

This is a continuation of application Ser. No. 07/709,849, filed Jun. 3, 1991 and now abandoned, which is a division of application Ser. No. 07/075,368, filed Jul. 20, 1987 and now abandoned, which is a continuation-in-part of application Ser. No. 06/845,097, filed Mar. 27, 1986 and now abandoned.

The invention relates to sulphonic acid group-free basic compounds useful for dyeing substrates such as paper, textiles and leather.

According to the invention there is provided 1:1 and 1:2 metal complexes of a compound in free base or acid addition salt form of formula I ##STR3## in which the R₁ 's are identical and are hydrogen, C₁₋₄ alkyl, C₅₋₆ cycloalkyl, phenyl, benzyl or phenylethyl;

each n, independently, is 0, 1 or 2;

each R₂, independently, is hydrogen, halogen, hydroxy, nitro, --COOH, C₁₋₄ alkyl or C₁₋₄ alkoxy;

the T's are identical and are hydrogen --CN; --COOR₄ ; --CON(R₅)₂ ; --SO₂ N(R₅)₂ ; ##STR4##

the X_(a) 's are identical and are --O--, --S-- or >N--R₅ ;

each R₃, independently, is hydrogen, C₁₋₄ alkyl, --N(R₅)₂ or --CON(R₅)₂ ;

the R₄ 's are identical and are C₁₋₆ alkyl or phenyl-C₁₋₃ alkyl;

each R₅, independently, is hydrogen or C₁₋₄ alkyl; or when two R₅ 's are attached to a nitrogen atom, both R₅ 's together with the N-atom to which they are attached may form a saturated ring which contains one to three hetero atoms and is unsubstituted or substituted by one to three C₁₋₄ alkyl groups;

the R₆ 's are identical and are C₁₋₄ alkyl;

the B's are identical and are --A₁ --NR₇ R₈ or --A₁ --.sup.⊕ NR₇ R₈ R₉ A.sup.⊖ ;

the A₁ 's are identical and are C₂₋₈ alkylene;

the R₇ 's are identical and are C₁₋₆ alkyl , C₂₋₆ alkyl monosubstituted by halogen, hydroxy or cyano; phenyl(C₁₋₃ alkyl) the phenyl ring of which is unsubstituted or substituted by 1 to 3 groups selected from halogen, C₁₋₄ alkyl and C₁₋₄ alkoxy; or C₅₋₆ cycloalkyl, unsubstituted or substituted by 1 to 3 C₁₋₄ alkyl groups;

the R₈ 's are identical and have one of the significances of R₇, independently,

or R₇ and R₈ together with the N-atom to which they are attached form a saturated ring which contains one to three hetero atoms and is unsubstituted or substituted by one to three C₁₋₄ alkyl groups or N'-aminoethylpiperazinium;

the R₉ 's are identical and are C₁₋₄ alkyl unsubstituted or substituted by phenyl, --CH₂ COCH₃, --CH₂ CONH₂ or --CH₂ --CHOH--CH₂ Cl;

or R₇, R₈, R₉ and the N-atom to which they are attached form a pyridinium group (attached by its N-atom) unsubstituted or substituted by one to three C₁₋₄ alkyl groups, a saturated ring which contains one to three hetero atoms and is unsubstituted or substituted by one to three C₁₋₄ alkyl groups or N--C₁₋₂ alkyl-N'-aminoethylpiperazinium;

X_(o), when all four groups R₂ are hydrogen, is selected from X₁ to X₆₃ and X₁₀₀ to X₁₀₉ ;

in which X₁ is a direct bond, X₂ is a linear or branched C₁₋₄ alkylene radical, ##STR5##

R₄₂ is halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy,

each R₄₃ independently is a linear or branched C₁₋₄ alkylene group, --CH₂ --CHOH--CH₂ --, --CH₂ CH₂ --CHOH--CH₂ -- or --CH(CH₃)--CHOH--CH₂ --,

each R₄₄ independently is hydrogen or C₁₋₄ alkyl group,

each g independently is 1, 2, 3 or 4,

each R₄₅ independently, is halogen, --NH--CH₂ --CH₂ --OH, --N(CH₂ --CH₂ --OH)₂, --NH₂, --OH, --NH--(CH₂)₂₋₃ N(C₂ H₅)₂, ##STR6##

or X_(o), when at least one R₂ is other than hydrogen, is selected from X₁, X₂, X₁₁, X₁₂, X₁₄, X₁₅, X₁₇ to X₂₁, X₂₅, X₂₇, X₃₂, X₃₄, X₅₇, X₆₂ and X₁₀₃ ; and

A.sup.⊖ is an anion.

g is preferably 1, 2 or 3.

Each R₄₃ independently is preferably linear or branched C₁₋₄ alkylene.

Furthermore, the invention provides

a) a metal-free compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(o) and n are as defined above, with the provisos that

1) both T's are other than cyano, --COOR₄, --CON(R₅)₂ and --SO₂ N(R₅)₂ in which each R₅ independently, is hydrogen or C₁₋₄ alkyl, when X_(o) is X₁, X₂, X₃, X₅, X₆, X₉, X₁₃ or X₂₁, and

2) both T's are other than --CN, --COOR₄ and --SO₂ N(R₅)₂ in which each R₅, independently, is hydrogen or C₁₋₄ alkyl, when X_(o) is X₃₁ or X₃₂ ;

b) a metal-free compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(o) and n are as defined above with the proviso that both T's are other than cyano, --COOR₄, --CON(R₅)₂ and --SO₂ N(R₅)₂ in which each R₅ independently, is hydrogen or C₁₋₄ alkyl;

c) a metal-free compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(o) and n are as defined above with the provisos that both T's are other than cyano, --COOR₄, --CON(R₅)₂ and --SO₂ N(R₅)₂ in which each R₅ independently is hydrogen or C₁₋₄ alkyl, and either

i) X_(o) is other than X₁ ; or

ii) X_(o) is other than X₂ ; or

iii) X_(o) is other than X₃ ; or

iv) X_(o) is other than X₅ ; or

v) X_(o) is other than X₆ ; or

vi) X_(o) is other than X₉ ; or

vii) X_(o) is other than X₁₃ ; or

viii) X_(o) is other than X₂₁ ;

d) a metal-free compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(o) and n are as defined above, with the provisos that both T's are other than cyano, --COOR₄ and --SO₂ N(R₅)₂ in which each R₅ independently is hydrogen or C₁₋₄ alkyl, and either

i ) X_(o) is other than X₃₁ ; or

ii) X_(o) is other than X₃₂ ;

e) a metal-free compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(o) and n are as defined above with the proviso that X_(o) is other than X₁, X₂, X₃, X₅, X₆, X₉, X₁₃, X₂₁, X₃₁ and X₃₂ ;

f) a 1:1 or 1:2 metal complex of a compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(o) and n are as defined above with the proviso that both T's are other than cyano, --COOR₄, --CON(R₅)₂ and --SO₂ N(R₅)₂ in which each R₅ independently, is hydrogen or C₁₋₄ alkyl;

g) a 1:1 or 1:2 metal complex of a compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(O) and n are as defined above with the provisos that both T's are other than cyano, --COOR₄, --CON(R₅)₂ and --SO₂ N(R₅)₂ in which each R₅ independently, is hydrogen or C₁₋₄ alkyl; and either

i) X_(o) is other than X₁ ; or

ii) X_(o) other than X₂ ; or

iii) X_(o) other than X₃ ; or

iv) X_(o) is other than X₅ ; or

v) X_(o) is other than X₆ ; or

vi) X_(o) is other than X₉ ; or

vii) X_(o) other than X₁₃ ; or

viii) X_(o) other than X₂₁ ;

h) a 1:1 or 1:2 metal complex of a compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(o) and n are as defined above with the provisos that both T's are other than cyano, --COOR₄ and --SO₂ N(R₅)₂ in which each R₅, independently, is hydrogen or C₁₋₄ alkyl, and either

i) X_(o) is other than X₃₁ ; or

ii) X_(o) is other than X₃₂ ;

i) a 1:1 or 1:2 metal complex of a compound of formula I, in free base or acid addition salt form, in which B, R₁, R₂, T, X_(o) and n are as defined above with the provisos that X_(o) is other than X₁, X₂, X₃, X₅, X₆, X₉, X₁₃, X₂₁, X₃₁ and X₃₂.

Any R₄₃ in a) to i) is independently preferably linear or branched C₁₋₄ alkylene.

For the avoidance of doubt in X_(o) where the bridging group is asymmetric, it can be attached to phenyl group D at either end. For the avoidance of doubt, a compound of formula I can be present in a mixture which may include one or more other compounds of formula I or not of formula I.

When the compounds of formula I are in 1:1 metal complex form, preferably the metal atom is copper, zinc, chromium, cobalt, nickel, iron or manganese and when the compounds of formula I are in 1:2 metal complex form, preferably the metal atom is chromium, nickel, cobalt or iron.

The alkylene group as A₁ may be linear or branched.

In the specification halogen means fluorine, chlorine, bromine, or iodine, preferably chlorine or bromine, particularly chlorine.

According to the invention, the molecule of a compound of formula I contains two identical pyridone coupling component residues. Depending on the significances of T and B, each pyridone residue of the molecule bears either one protonatable basic group optionally together with a quaternary ammonium group or one or two quaternary ammonium groups.

The term "protonatable basic group" includes protonatable primary, secondary and tertiary amino groups.

R₁ is preferably R₁ ' where R₁ ' is methyl, ethyl, phenyl, benzyl or cyclohexyl. More preferably R₁ is R₁ " where R₁ " is methyl or phenyl, especially methyl.

R₂ is preferably R₂ ' where R₂ ' is hydrogen methyl ethyl hydroxy methoxy ethoxy chlorine or bromine R₂ is more preferably R₂ " where R₂ " is hydrogen, hydroxy, methyl, methoxy, ethoxy or chlorine. Most preferably R₂ is R₂ '" where R₂ '" is hydrogen, hydroxy, methoxy or ethoxy. R₂ is also preferably R_(2a) ", where R_(2a) " is hydrogen, hydroxy, methyl, methoxy or chlorine, especially hydrogen.

Among the significances of T, the significance of cyano is less preferred, particularly when X_(o) is X₉, X₂₁, X₃₁, X₃₂, X₃₄, X₃₅, X₃₆, X₃₇ and X₅₅.

T is preferably T' where T' is hydrogen, --CN, --CON(R₅ ')₂, where R₅ ' is as defined below, or ##STR7## where R₃ ' is as defined below. More preferably T is T" where T" is hydrogen, --CN, --CONH₂ or ##STR8## where R₃ " is as defined below.

Most preferably T is T'" where T'" is hydrogen, ##STR9##

Preferably R₃ is R₃ ' where R₃ ' is hydrogen, methyl, ethyl, --NH₂ or --N(CH₃)₂. More preferably R₃ is R₃ " where R₃ " is hydrogen or methyl.

Preferably R₅ is R₅ ' where R₅ ' is hydrogen methyl or ethyl, or when two R₅ groups are attached to a nitrogen atom, both R₅ ' groups together with the N-atom may form an unsubstituted pyrrolidinyl, piperidino, morpholino, piperazinyl or N-methylpiperazinyl radical. More preferably R₅ is hydrogen.

B is preferably B' where B' is --A₁ '--NR₇ 'R₈ ' or --A₁ '--.sup.⊕ NR₇ 'R₈ 'R₉ 'A.sup.⊖ where the symbols are as defined below. More preferably B is B" where B" is --(CH₂)₂ --NR₇ "R₈ ", --(CH₂)₃ --NR₇ "R₈ ", --(CH₂)₂ --NR₇ "R₈ "R₉ "A.sup.⊖ or --(CH₂)₃ --.sup.⊕ NR₇ "R₈ "R₉ " A.sup.⊖ where the symbols are as defined below. Most preferably B is B'" where B'" is --(CH₂)₂ --K or --(CH₂)₃ --K, the symbol K being selected from ##STR10##

B is also preferably B_(a) '" where B_(a) '" is --(CH₂)₂ --K_(a) or --(CH₂)₃ --K_(a), the symbol Ka having one of the significances given above for K or being ##STR11##

A₁ is preferably A₁ ' where A₁ ' is --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, ##STR12##

Preferably R₇ is R₇ ' where R₇ ' is linear or branched C₁₋₆ alkyl unbranched hydroxyC₂₋₃ alkyl, benzyl, 2-chloroethyl or 2-cyanoethyl.

More preferably R₇ is R₇ " where R₇ " is methyl or ethyl.

Preferably R₈ is R₈ ' where R₈ ' has one of the significances of R₇ ', independently, and R₉ is R₉ ' where R₉ ' is methyl, ethyl, propyl or benzyl.

More preferably R₈ is R₈ " where R₈ " has one of the significances of R₇ " and R₉ is R₉ " where R₉ " is methyl ethyl or benzyl

R₇ ' and R₈ ' together with the N-atom to which they are attached may also form a pyrrolidinyl, piperidino, morpholino, piperazinyl, N-methylpiperazinyl or N-aminoethylpiperazinyl group.

R₇ ', R₈ ' and R₉ ' together with the N-atom to which they are attached may also form a pyridinium ring unsubstituted or substituted by one or two methyl groups or a radical β ##STR13## where Z_(o) is a direct bond, --CH₂ --, --O--, --S--, --SO₂ --, --SO--, --NH--, >N-R₁₀, .sup.⊕ N--(R₁₀)₂ A.sup.⊖ or >N-C₂ H₄ --NH₂, and each R₁₀, independently, is methyl or ethyl.

R₇ " and R₈ " together with the N-atom to which they are attached may also form a morpholino, piperidino, piperazinyl, N-methylpiperazinyl or N-aminoethylpiperazinyl group.

R₇ ", R₈ " and R₉ " together with the N-atom to which they are attached may also form a pyridinium, 2- or 3-picolinium, N-methylmorpholinium, N-methylpiperidinium, N-methylpiperazinium, N,N'-dimethylpiperazinium, N-methyl-N'-(2-aminoethyl)piperazinium or N,N',N'-trimethylpiperazinium A.sup.⊖ group may also form a N,N',N'-trimethylpiperazinium group.

X_(o) is preferably X_(o) ' where X_(o) ' when all four R₂ 's are hydrogen, is selected from X₁, X₅, X₆, X₇, X₁₀, X₁₁, X₁₂, X₁₆, X₁₇, X₂₂, X₂₅, X₂₆, X₂₇, X₃₀, X₃₁, X₄₉, X₅₀, X₅₁, X₅₃, X₅₄, X₅₈, X₅₉, X₆₂, X₁₀₁ (where R₄₃ is --(CH₂)₁₋₂), X₁₀₃ (where R₄₃ is --(CH₂)₁₋₂ and R₄₅ is --NH(CH₂)₂₋₃ --N(C₂ H₅)₂), X₁₀₄ (where R₄₄ =H and g=2 or 3), X₁₀₈ (where R₄₃ =--(CH₂)₁₋₃ --), X₇₀₋₉₀ and X₁₁₀, where X₇₀₋₉₀ and X₁₁₀ are as defined below: ##STR14## or X_(o) ', when at least one R₂ is other than hydrogen, is X₁, X₁₁, X₁₂, X₁₇, X₆₂, X₇₀, X₇₁, X₇₄, X₇₉, X₈₀, X₈₁, X₈₂, X₈₅, X₈₆, X₈₈ or X₁₀₃ where R₄₃ is --(CH₂)₁₋₂ -- as defined above, or X_(o) ', when at least one R₂ is other than hydrogen, is also X_(oa) ' where X_(oa) ' is X₁, X₁₁, X₁₂, X₁₇, X₂₇, X₃₁, X₆₂, X₇₀, X₇₁, X₇₄, X₇₉, X₈₀, X₈₁, X₈₂, X₈₃, X₈₅, X₈₆, X₈₈, X₈₉ or X₁₀₃ (where R₄₃ is --(CH₂)₁₋₂ --) as defined above,

where R_(42a) is hydrogen, Cl, CH₃ or OCH₃, and R_(45a) is Cl, --NH(CH₂)₂ OH, methoxy, hydroxy, --NH₂, ethoxy, --NH(CH₂)₃ N(C₂ H₅)₂, --N(CH₂ CH₂₀ OH)₂, ##STR15##

When X_(o) ' is X₃₁, X₇₉, X₈₀, X₈₆ or X₈₉, both T's are preferably hydrogen, --CON(R₅ ')₂ or ##STR16##

More preferably X_(o) is X_(o) " when all four R₂ 's are hydrogen, X_(o) " being X₁, X₁₁, X₁₇, X₂₇, X₅₁, X₅₃, X₅₄, X₆₂, X₇₀ to X₇₇, X₇₉, X₈₀, X₈₁, X₈₂, X₈₅ to X₉₀ or X₁₁₀, especially X₁₁, X₁₇, X₈₁, X₈₂, X₈₅, X₈₆ or X₈₉.

When at least one R₂ is other than hydrogen, then X_(o) is preferably X_(o) " where X_(o) " is X₁₁, X₁₇, X₂₇, X₆₂, X₈₁, X₈₂, X₈₃, X₈₅, X₈₆ or X₈₉.

In the compounds of formula I, preferably each ring D or D₁, independently, in addition to X_(o) and the azo group, bears either one further substituent, preferably a methoxy, ethoxy or hydroxy group, especially in a position ortho to the azo group, or no further substituent. More preferably, when further substituted, at least one of rings D and D₁ is further substituted by hydroxy or both rings D and D₁ are each further substituted by methoxy.

X_(o) is preferably attached in the 2-, 3- and/or 4-positions, particularly the 3 and/or 4-positions on the rings D and D₁.

Each ring D or D₁ may also bear two substituents R₂, in which case one R₂ is preferably a metallisable group and the other is halogen or C₁₋₄ alkyl.

Preferred compounds of the invention are the 1:1 and 1:2 metal complexes of compounds in free base or acid addition salt form, of formula II ##STR17## where the symbols R₁ ', T', B', R₂ ' and X_(o) are as defined above

More preferred compounds of the invention are 1:1 or 1:2 metal complex of a compound,in free base or acid addition salt form, of formula III ##STR18## in which the R₁ ", R_(2a) ", T", B" and X_(o) ' are as defined above,

X_(o) ' being attached in the 3- or 4-position (shown) on rings D' and D₁ '.

The following groups of compounds are further preferred:

a) metal-free compounds of formula II and formula III, in free base or acid addition salt form, in which the B', B", R₁ ', R₁ ", R₂ ', R_(2a) ", T', T", X_(o) and X_(o) ' are as defined above,

with the provisos that

both T''s are other than cyano or --CCN(R₅ ')₂ in which each R₅ ' independently is hydrogen, methyl or ethyl when X_(o) is X₁, X₂, X₃, X₅, X₆, X₉, X₁₃ or X₂₁, and both T''s are other than cyano when X_(o) is X₃₁ or X₃₂ ;

or, in the case of formula III, both T"'s are other than cyano or --CONH₂ when X_(o) ' is X₁, X₅, X₆, X₇₀, X₇₈ or X₈₁ to X₈₄ and both T"'s are other than cyano when X_(o) ' is X₃₁, X₇₉ and X₈₀ ;

b) metal-free compounds of formula II and formula III, in free base or acid addition salt form, in which B', B", R₁ ', R₁ ", R₂ ', R_(2a) ", T', T", X_(o) and X_(o) ' are as defined above,

with the proviso that

both T''s are other than cyano or --CON(R₅ ')₂ in which each R₅ ' independently is hydrogen, methyl or ethyl,

or, in the case of formula III, both T"'s are other than cyano or --CONH₂ ;

c) metal-free compounds of formula II and formula III, in free base or acid addition salt form, in which B', B", R₁ ', R₁ ", R₂ ', R_(2a) ", T', T", X_(o) and X_(o) ' are as defined above,

with the provisos that in the case of formula II, both T''s are other than cyano or --CON(R₅ ')₂ in which each R₅ ' independently is hydrogen, methyl or ethyl and either

i) X_(o) is other than X₁ ; or

ii) X_(o) is other than X₂ ; or

iii) X_(o) is other than X₃ ; or

iv) X_(o) is other than X₅ ; or

v) X_(o) is other than X₆ ; or

vi) X_(o) is other than X₉ ; or

vii) X_(o) is other than X₁₃ ; or

viii) X_(o) is other than X₂₁ ; or

or, in the case of formula III, both T"'s are other than cyano or --CONH₂ and either

i) X_(o) ' is other than X₁ ; or

ii) X_(o) ' is other than X₅ ; or

iii) X_(o) ' is other than X₆ ; or

iv) X_(o) ' is other than X₇₀ ; or

v) X_(o) ' is other than X₇₈ ; or

vi) X_(o) ' is other than X₈₁ to X₈₄ ;

d) metal-free compounds of formula II and formula III, in free base or acid addition salt form, in which B', B", R₁ ', R₁ ", R₂ ', R_(2a) ", T', T", X_(o) and X_(o) ' are as defined above,

with the provisos that in the case of formula II, both T''s are other than cyano and either

i) X_(o) is other than X₃₁ ; or

ii) X_(o) is other than X₃₂ ;

or, in the case of formula III, both T"'s are other than cyano and either

i) X_(o) ' is other than X₃₁ ; or

ii) X_(o) ' is other than X₇₉ or X₈₀ ;

e) metal-free compounds of formula II and formula III, in free base or acid addition salt form, in which B', B", R₁ ', R₁ ", R₂ ', R_(2a) ", T', T", X_(o) and X_(o) ' are as defined above,

with the proviso that

X_(o) is other than X₁, X₂, X₃, X₅, X₆, X₉, X₁₃, X₂₁, X₃₁ or X₃₂,

or, respectively, X_(o) ' is other than X₁, X₅, X₆, X₃₁, X₇₀ and X₇₈ to X₈₄ ;

f) 1:1 and 1:2 metal complexes of compounds of formula II or formula III, in free base or acid addition salt form, in which B', B", R₁ ', R₁ ", R₂ ', R_(2a) ", T', T", X_(o) and X_(o) ' are as defined above,

with the proviso that

both T''s are other than cyano or --CON(R₅ ')₂ in which each R₅ ' independently is hydrogen, methyl or ethyl,

or, respectively, both T"'s are other than cyano or --CONH₂ ;

g) 1:1 and 1:2 metal complexes of compounds of formula II or formula III, in free base or acid addition salt form, in which B', B", R₁ ', R₁ ", R₂ ', R_(2a) ", T', T", X_(o) and X_(o) ' are as defined above,

with the provisos that in the case of formula II, both T''s are other than cyano or --CON(R₅ ')₂ in which each R₅ ' independently is hydrogen, methyl or ethyl and either

i) X_(o) is other than X₁ ; or

ii) X_(o) is other than X₂ ; or

iii) X_(o) is other than X₃ ; or

iv) X_(o) is other than X₅ ; or

v) X_(o) is other than X₆ ; or

vi) X_(o) is other than X₉ ; or

vii) X_(o) is other than X₁₃ ; or

viii) X_(o) is other than X₂₁ ; or

or, in the case of formula III, both T"'s are other than cyano or --CONH₂ and either

i) X_(o) ' is other than X₁ ; or

ii) X_(o) ' is other than X₅ ; or

iii) X_(o) ' is other than X₆ ; or

iv) X_(o) ' is other than X₇₀ ; or

v) X_(o) ' is other than X₇₈ ; or

vi) X_(o) ' is other than X₈₁ to X₈₄ ;

h) 1:1 and 1:2 metal complexes of the compounds formula II or formula III, in free base or acid addition salt form, in which B', B", R₁ ', R₁ ", R₂ ', R_(2a) ", T', T", X_(o) and X_(o) ' are as defined above,

with the provisos that in the case of formula II, both T''s are other than cyano and either

i ) X_(o) is other than X₃₁ ; or

ii) X_(o) is other than X₃₂ ;

or, in the case of formula III, both T"'s are other than cyano and either

i ) X_(o) ' is other than X₃₁ ; or

ii) X_(o) ' is other than X₇₉ or X₈₀ ; and

i) 1:1 and 1:2 metal complexes of the compounds formula II or formula III, in free base or acid addition salt form, in which the symbols B', B", R₁ ', R₁ ", R₂ ', R2a", T', T", X_(o) and X_(o) ' are as defined above,

with the proviso that

X_(o) is other than X₁, X₂, X₃, X₅, X₆, X₉, X₁₃, X₂₁, X₃₁ or X32,

or, respectively, X_(o) ' is other than X₁, X₅, X₆, X₃₁, X₇₀ and X₇₈ to X₈₄.

In the compounds of formulae II and III according to groups a) and d) and in the 1:1 and 1:2 metal complexes according to group h), both T''s , respectively both T"'s, are preferably hydrogen or ##STR19## more preferably when X_(o) is X₂, X₁₁, X₁₇, X₃₁, X₃₂ or X₃₄, respectively, when X_(o) ' is X₃₁, X₇₉, X₈₀ to X₈₆, X₈₈ or X₈₉.

Further preferred compounds of formula I are those, in free base or acid addition salt form, of formula IV ##STR20## in which T'", B'" and X_(o) " are as defined above. Compounds of formula IV in which both B'"'s have one of the significances of B_(a) '" are also preferred.

Other preferred compounds of formula I are those, in free base or acid addition salt form, of formula IVa ##STR21## in which T"', B"', R₂ "' and X_(o) " are as defined above. Particularly preferred compounds of formula IVa are those wherein both B"''s are --(CH₂)₂₋₃ --K, K being --N(CH₃)₂ or --N(C₂ H₅)₂, and X_(o) " is X₁₁, X₁₇, X₈₁, X₈₂, X₈₃, X₈₅, X₈₆ or X₈₉.

Interesting compounds of formula I in 1:1 metal complex form and in free base or acid addition salt form are of formula V ##STR22## in which each R_(2a), independently, is hydrogen, halogen or C₁₋₄ alkyl;

Me is copper, chromium, manganese, cobalt or nickel, and B, T, R₁ and X_(o) are as defined above.

Preferably Me is copper.

Preferred compounds of formula I in 1:1 metal complex form and in free base or acid addition salt form are of formula VI ##STR23## In which R₁, R₂, R_(2a), T, B and X_(o) are as defined above, and Me₁ is copper.

Most preferred compounds of formula I in 1:1 metal complex form are those of formula VI in which R₁ is R₁ ', particularly R₁ ", especially methyl; T is T', particularly T"; especially T'", R₂ and R_(2a) are hydrogen; B is B', preferably B", particularly B'"; and X_(o) and X_(o) ', particularly X_(o) ".

Preferred compounds of formula I in 1:2 metal complex form and in free base or acid addition salt form are of formula VII ##STR24## in which R₁, R₂, R_(2a), T, B and X_(o) are as defined above, and

Me₂ is chromium, cobalt or iron.

Most preferred compounds of formula I in 1:2 metal complex form are those of formula VII in which R₁ is R₁ +, particularly R₁ ", especially methyl; T is T', particularly T", especially T"'; R₂ and R_(2a) are hydrogen; B is B', preferably B", particularly B"', and X_(o) is X_(o) ', particularly X_(o) ".

Any R₄₃ in formulae II-VII, the preferences thereof and groups a) -i) following formulae II and VII is independently preferably linear or branched C₁₋₄ alkylene.

Further, according to the invention there is provided a process for preparing compounds of formula I as defined above comprising coupling to 1 mole of a tetrazotised compound of a diamine of formula VIII ##STR25## in which R₂, n and X_(o) are as defined above, 2 moles of a compound of formula IX ##STR26## in which R₁, B and T are as defined above, and, if required, the resulting compounds of formula I may be converted into the corresponding 1:1 or 1:2 metal complex form, and/or into the corresponding acid addition salt form.

Compounds of formulae VIII and IX are known or may be made by known methods from known compounds.

Coupling to form compounds of formula I can be carried out according to known methods. Advantageously, coupling is carried out in aqueous (acid, neutral or alkali) medium at a temperature from -10° C. to room temperature, if necessary, in the presence of a coupling accelerator such as pyridine or urea. Alternatively, coupling may be effected in a mixture of solvents, for example, water and an organic solvent.

Metallisation of the compounds of formula I can be achieved by known methods.

The disazo compounds of formula I in 1:1 metal complex form may be prepared by metallising compounds of formula I in metal-free form with a metal selected from copper, cobalt, iron, nickel, manganese, chromium and zinc.

The disazo compounds of formula I in 1:2 metal complex form may be prepared by metallising compounds of formula I in metal-free form with a metal selected from chromium, nickel, cobalt and iron.

A further method for the preparation of disazo compounds of formula I in 1:2 metal complex form is by reacting a compound of formula I or other than formula I in metal-free form with a disazo compound 1:1 metal complex of formula I when the metal is chromium, nickel, cobalt or iron.

The metallisation process to form a 1:1 metal complex of the type of formula VI is advantageously carried out by treating 1 mole of a disazo compound with a metallising agent containing 1 equivalent of metal.

1:1 Metal complex formation using copper can be carried out by directly reacting a compound of formula I with metal salt or by oxidative coppering preferably at 40°-70° C. and at a pH of 4-7 in the presence of a Cu(II) salt or with copper filings in the presence of H₂ O₂ or any other oxidizing material; or demethylating coppering can be carried out in a pH range of 3-4 at a high temperature.

Metallisation is carried out advantageously in aqueous medium or in a mixture of water and a water-miscible organic solvent, for example acetone, lower alkyl alcohols, dimethylformamide, formamide, glycols or acetic acid at a pH range from 1.0 to 8.0, preferably pH 2 to 7. The metallisation process may be carried out at a temperature from room temperature to the boiling point of the reaction medium.

Alternatively, metallisation may be effected in a wholly organic medium (for example dimethylformamide). Advantageously, for instance, cobaltisation may be carried out in the presence of an inorganic nitrite such as lithium, sodium, ammonium or potassium nitrite in the ratio of 2 to 6 moles of nitrite per gram atom of cobalt.

Suitable cobalt-yielding compounds are, for example, cobalt(II) and Co(III) sulphate, acetate, formate and chloride.

Copper-yielding compounds are, for example, cupric sulphate, cupric formate, cupric acetate and cupric chloride.

The nickel-yielding compounds are Ni(II) or Ni(III) compounds, such as nickel formate, nickel acetate and nickel sulphate.

Preferred manganese-yielding compounds are Mn(II) compounds and iron-yielding compounds are Fe(II) or Fe(III) compounds. Examples of these and zinc-yielding compounds are manganese, iron and zinc formate, acetate and sulphate.

Preferred chromium-yielding compounds are Cr(II) and Cr(III) formate, acetate and sulphate.

In the compounds of formula I the anions A.sup.⊖ can be any nonchromophoric anions such as those conventional in basic dyestuff chemistry. Suitable anions include chloride, bromide, sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate, benzene-sulphonate, oxalate, maleate, acetate, propionate, lactate, succinate, tartrate, malate, methane-sulphonate and benzoate as well as complex anions, for example zinc chloride double salts and anions of boric acid, citric acid, glycollic acid, diglycollic acid and adipic acid or addition products of ortho boric acids with polyalcohols with at least one cis diol group present. These anions can be exchanged for each other by ion exchange resins on reaction with acids or salts (for example via the hydroxide or bicarbonate) or according to German Offenlegungsschrift 2,001,748 or 2,001,816.

The compounds of the invention are suitable for dyeing, padding or printing fibres, threads or textile materials, particularly natural or regenerated cellulose materials for example cotton, polyester or synthetic polyamides modified by anionic groups. Such polyesters and polyamides are described in Belgian Patent 706,104 and U.S. Pat. No. 3,379,723.

The compounds of the invention are also used for dyeing, padding or printing fibres, threads or textiles produced therefrom which consist of or contain homo- or mixed polymers of acrylonitrile or of 1,1-dicyanoethylene.

The textile material is dyed, printed or pad-dyed in accordance with known methods. Acid modified-polyamide is dyed particularly advantageously in an aqueous, neutral or acid medium, at temperatures of 60° C. to boiling point or at temperatures above 100° C. under pressure.

The textile material may also be dyed by the compounds of formula I in organic solvents, e.g. in accordance with the directions given in German Offenlegungsschrift 2,437,549.

Cellulose material is mainly dyed by the exhaust process, i.e. from a long or short bath, at room temperature to boiling temperature, optionally under pressure, whereby the ratio of the bath is from 1:1 to 1:100 and preferably from 1:20 to 1:50. If dyeing is effected from a short bath, then the liquor ratio is 1:3 to 1:15. The pH of the dyebath varies between 3 and 10 (for short and long dyebaths).

Printing may be effected in accordance with known methods.

The dyestuffs of the invention are particularly suitable for dyeing or printing paper, e.g. for the production of bulk-dyed, sized and unsized paper. The dyestuffs may similarly be used for dyeing paper by the dipping process. The dyeing of paper is effected by known methods. The compounds of the invention are especially suitable for dyeing ligneous fibre materials, particularly bleached or unbleached mechanical wood pulp paper, thermomechanical pulp, unbleached cellulose, waste paper and china clay, calcium carbonate and talcum.

The azo compounds of the invention may also be applied to bast fibres such as hemp, flax, sisal, jute, coir or straw.

The dyestuffs of the invention are also suitable for dyeing or printing leather by known methods and dyeings with good fastness properties are obtained.

Dyeings prepared with dyestuffs of the invention on ligneous fibre materials produce a substantially clear waste liquor which is important for environmental reasons. The dyestuffs of the invention have good build-up properties, do not bleed once applied to ligneous fibre substances and are not pH sensitive. They have a high affinity for ligneous fibre materials, particularly bleached or unbleached mechanical wood pulp paper and unbleached cellulose and do not mottle on mechanical wood pulp paper. Dyeings produced with dyestuffs of the invention have good light fastness and the nuance on exposure for a long time to light fades tone in tone. The dyestuffs of the invention have good wet-fastness properties not only for water but also for milk, soap, water, sodium chloride solution, urine, fruit juice and sweetened mineral water. Further dyeings made with dyestuffs of the invention are fast to alcoholic beverages due to good alcohol fastness. Further, the dyestuffs of the invention have good light stability.

The compounds of the invention are advantageously used in their acid addition salt form, e.g. a salt produced by addition of a carboxylic acid such as acetic acid, lactic acid, formic acid, methoxyacetic acid, ethoxyacetic acid or glycollic acid, or quaternary ammonium salt form.

For their use the azo compounds of the invention are suitably worked up into stable solid or liquid preparations, according to known methods, advantageously by grinding or granulating or by dissolving in suitable solvents, optionally adding an assistant, e.g. a stabiliser, a solubilising or a diluting agent such as urea. Such preparations may be obtained, for example, as described in French Patent Specifications 1,572,030 and 1,581,900 or in accordance with German DOS 2,001,748 and 2,001,816.

Liquid dyeing compositions are preferably as follows:

1 part by weight of a compound of formula I (in acid addition salt form or quaternary ammonium salt form);

0.01-1 part by weight of an inorganic salt (preferably 0.1 part);

0.01-1 part by weight of an organic acid such as formic, acetic, lactic, citric, propionic or methoxyacetic acid;

1-8 parts by weight of water; and

0-5 parts by weight of a solubilising agent such as a glycol (diethylene glycol, triethylene glycol or hexylene glycol ), a glycol ether such as methyl cellosolve methylcarbitol, butylpolyglycol, urea, formamide and dimethylformamide.

Solid dyeing preparations are preferably as follows:

1 part by weight of a compound of formula I (in acid addition salt form or quaternary ammonium salt form)

0.01-1 part by weight of an inorganic salt (preferably 0.01 to 0. 1 part) and

0-8 parts by weight of a diluting agent such as urea, dextrin, glucose or d-glucose).

The solid compositions may usually contain up to 10% water.

The entire specification of great-grandparent application Ser. No. 06/845,097 (including the claims), particularly pages 1 to 16, is hereby incorporated by reference as if set forth herein in its entirety.

The invention will now be illustrated by the following Examples in which all parts are by weight and all temperatures are in degrees Celsius.

EXAMPLE 1

19.8 Parts (0.1M) of 4,4'-diaminodiphenylmethane are tetrazotised according to known methods with 13.8 parts (0.2M) of sodium nitrite at 0°-5° in 200 parts of water and 60 parts of 30% hydrochloric acid. 64.4 Parts (0.2M) of a compound of the formula ##STR27##

dissolved in 250 parts of water are added over 30 minutes to the ice cold tetrazotised solution. By the addition of a 30% NaOH solution the pH is brought to 4.5. The resulting dyestuff is of formula 1b ##STR28## and is in solution.

By concentration under vacuum or by precipitation in acetone/alcohol the dyestuff is isolated.

The reaction mixture however can be used directly for dyeing without isolating the product.

The dyestuff of formula 1b has a high solubility in water and gives yellow dyeings with good fastness properties.

EXAMPLES 2 TO 86

Compounds of the formula ##STR29## in which the symbols are defined in Table I below, wherein the asterisked atom is attached to phenyl ring D, can be produced by a method analogous to that of Example 1 from appropriate reactants. ##STR30##

    __________________________________________________________________________                               position of X.sub.o on                                                                   Shade of                                   Ex.                                                                               T B X.sub.o            ring D and ring D.sub.1                                                                  the dyeing                                 __________________________________________________________________________      2 T.sub.4                                                                          B.sub.1                                                                                             (4,4')    yellow                                      3 T.sub.4                                                                          B.sub.4                                                                           ##STR31##         (4,4')    yellow                                      4 T.sub.5                                                                          B.sub.1                                                                           ##STR32##         (4,4')    yellow                                      5 T.sub.5                                                                          B.sub.2                                                                           ##STR33##         (4,4')    yellow                                      6 T.sub.5                                                                          B.sub.3                                                                           ##STR34##         (4,4')    yellow                                      7 T.sub.5                                                                          B.sub.4                                                                           ##STR35##         (4,4')    yellow                                      8 T.sub.6                                                                          B.sub.4                                                                           ##STR36##         (4,4')    yellow                                      9 T.sub.7                                                                          B.sub.4                                                                           ##STR37##         (4,4')    yellow                                     10 T.sub.8                                                                          B.sub.4                                                                           ##STR38##         (4,4')    yellow                                     11 T.sub.4                                                                          B.sub.2                                                                           ##STR39##         (4,4')    yellow                                     12 T.sub.4                                                                          B.sub.2                                                                          S                  (4,4')    yellow                                     13 T.sub.4                                                                          B.sub.2                                                                          NH                 (4,4')    blue                                       14 T.sub.4                                                                          B.sub.2                                                                          O                  (4,4')    orange                                     15 T.sub.4                                                                          B.sub.2                                                                          SO.sub.2           (4,4')    yellow                                     16 T.sub.4                                                                          B.sub.2                                                                          NHCONH             (4,4')    red                                        17 T.sub.4                                                                          B.sub.1                                                                          NHCONH             (3,3')    yellow                                     18 T.sub.4                                                                          B.sub.2                                                                          CONH               (4,4')    orange                                     19 T.sub.5                                                                          B.sub.2                                                                           ##STR40##         (4,4')    orange                                     20 T.sub.4                                                                          B.sub.4                                                                           ##STR41##         (4,4')    orange                                     21 T.sub.5                                                                          B.sub.4                                                                           ##STR42##         (4,4')    orange                                     22 T.sub.4                                                                          B.sub.2                                                                           ##STR43##         (4,3')    yellow                                     23 T.sub.5                                                                          B.sub.4                                                                           ##STR44##         (4,3')    yellow                                     24 T.sub.4                                                                          B.sub.4                                                                           ##STR45##         (4,3')    yellow                                     25 T.sub.5                                                                          B.sub.2                                                                           ##STR46##         (3,3')    yellow                                     26 T.sub.4                                                                          B.sub.1                                                                           ##STR47##         (4,4')    red                                        27 T.sub.5                                                                          B.sub.4                                                                           ##STR48##         (4,4')    red                                        28 T.sub.4                                                                          B.sub.2                                                                           ##STR49##         (4,4' )   red                                        29 T.sub.4                                                                          B.sub.1                                                                           ##STR50##         (3,3')    yellow                                     30 T.sub.5                                                                          B.sub.2                                                                           ##STR51##         (4,4')    red                                        31 T.sub.1                                                                          B.sub.2                                                                           ##STR52##         (4,4')    yellow                                     32 T.sub.1                                                                          B.sub.5                                                                           ##STR53##         (4,4')    yellow                                     33 T.sub.4                                                                          B.sub.2                                                                          CH.sub.2 CH.sub.2  (4,4')    yellow                                     34 T.sub.4                                                                          B.sub.2                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     35 T.sub.4                                                                          B.sub.2                                                                          CONHCH.sub.2 CHOHCH.sub.2 NHCO                                                                    (4,4')    yellow                                     36 T.sub.4                                                                          B.sub.2                                                                           ##STR54##         (4,3')    yellow                                     37 T.sub.4                                                                          B.sub.2                                                                          NHCONH             (3,3')    yellow                                     38 T.sub.4                                                                          B.sub.4                                                                          OCH.sub.2 O        (4,4')    orange                                     39 T.sub.1                                                                          B.sub.2                                                                          NH                 (4,4')    blue                                       40 T.sub.4                                                                          B.sub.2                                                                          SS                 (4,4')    orange                                     41 T.sub.1                                                                          B.sub.2                                                                          CH.sub.2           (4,4')    yellow                                     42 T.sub.1                                                                          B.sub.6                                                                           ##STR55##         (4,4')    yellow                                     43 T.sub.1                                                                          B.sub.5                                                                          CH.sub.2           (4,4')    yellow                                     44 T.sub.1                                                                          B.sub.7                                                                           ##STR56##         (4,4')    yellow                                     45 T.sub.1                                                                          B.sub.2                                                                          CH.sub.2 CH.sub.2  (4,4')    yellow                                     46 T.sub.1                                                                          B.sub.6                                                                          CH.sub.2           (4,4')    yellow                                     47 T.sub.1                                                                          B.sub.5                                                                          CH.sub.2 CH.sub.2  (4,4')    yellow                                     48 T.sub.1                                                                          B.sub.7                                                                          CH.sub.2           (4,4')    yellow                                     49 T.sub.1                                                                          B.sub.2                                                                          CONH               (4,4')    yellow                                     50 T.sub.3                                                                          B.sub.5                                                                          CONH               (4,4')    yellow                                     51 T.sub.1                                                                          B.sub.2                                                                           ##STR57##         (4,3')    yellow                                     52 T.sub.1                                                                          B.sub.2                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     53 T.sub.3                                                                          B.sub.2                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     54 T.sub.1                                                                          B.sub.5                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     55 T.sub.3                                                                          B.sub.5                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     56 T.sub.1                                                                          B.sub.2                                                                          S                  (4,4')    yellow                                     57 T.sub.3                                                                          B.sub.2                                                                          S                  (4,4')    yellow                                     58 T.sub.1                                                                          B.sub.5                                                                          S                  (4,4')    yellow                                     59 T.sub.1                                                                          B.sub.6                                                                          S                  (4,4')    yellow                                     60 T.sub.1                                                                          B.sub.7                                                                          S                  (4,4')    yellow                                     61 T.sub.4                                                                          B.sub.5                                                                           ##STR58##         (4,4')    yellow                                     62 T.sub.1                                                                          B.sub.5                                                                           ##STR59##         (4,3')    yellow                                     63 T.sub.3                                                                          B.sub.2                                                                           ##STR60##         (4,3')    yellow                                     64 T.sub.3                                                                          B.sub.5                                                                           ##STR61##         (4,3')    yellow                                     65 T.sub.1                                                                          B.sub.6                                                                           ##STR62##         (4,3')    yellow                                     66 T.sub.4                                                                          B.sub.6                                                                           ##STR63##         (4,3')    yellow                                     67 T.sub.1                                                                          B.sub.7                                                                           ##STR64##         (4,3')    yellow                                     68 T.sub.4                                                                          B.sub.7                                                                           ##STR65##         (4,3')    yellow                                     69 T.sub.1                                                                          B.sub.6                                                                          CH.sub.2 CH.sub.2  (4,3')    yellow                                     70 T.sub.4                                                                          B.sub.6                                                                          CH.sub.2 CH.sub.2  (4,3')    yellow                                     71 T.sub.1                                                                          B.sub.7                                                                          CH.sub.2 CH.sub.2  (4,3')    yellow                                     72 T.sub.4                                                                          B.sub.7                                                                          CH.sub.2 CH.sub.2  (4,3')    yellow                                     73 T.sub.1                                                                          B.sub.6                                                                          CONHCH.sub.2 CHOHCH.sub.2 NHCO                                                                    (4,4')    yellow                                     74 T.sub.4                                                                          B.sub.6                                                                          CONHCH.sub.2 CHOHCH.sub.2 NHCO                                                                    (4,4')    yellow                                     75 T.sub.1                                                                          B.sub.7                                                                          CONHCH.sub.2 CHOHCH.sub.2 NHCO                                                                    (4,4')    yellow                                     76 T.sub.4                                                                          B.sub.7                                                                           CONHCH.sub.2 CHOHCH.sub.2 NHCO                                                                   (4,4')    yellow                                     77 T.sub.4                                                                          B.sub.6                                                                          CH.sub.2           (4,4')    yellow                                     78 T.sub.4                                                                          B.sub.7                                                                          CH.sub.2           (4,4')    yellow                                     79 T.sub.1                                                                          B.sub.6                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     80 T.sub.4                                                                          B.sub.6                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     81 T.sub.1                                                                          B.sub.7                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     82 T.sub.4                                                                          B.sub.7                                                                          CONHCH.sub.2 CH.sub.2 NHCO                                                                        (4,4')    yellow                                     83 T.sub.1                                                                          B.sub.2                                                                           ##STR66##         (3,3')    yellow                                     84 T.sub.1                                                                          B.sub.5                                                                           ##STR67##         (3,3')    yellow                                     85 T.sub.1                                                                          B.sub.7                                                                           ##STR68##         (3,3')    yellow                                     86 T.sub.1                                                                          B.sub.6                                                                           ##STR69##         (3,3')    yellow                                     __________________________________________________________________________

EXAMPLE 87

By following the procedure disclosed in Example 1 but using 4,4'-diamino-2,2'-dimethoxydiphenylmethane instead of 4,4'-diaminodiphenylmethane, the following dyestuff is obtained. ##STR70##

It has a high solubility in water and gives orange dyeings with good fastness properties.

Compounds of the formula ##STR71## in which the symbols are defined in Table II below can be produced by an analogous method to that of Example 1 from appropriate reactants.

                  TABLE II                                                         ______________________________________                                         Ex.     T     B        X.sub.o                                                                               shade of the dyeing                              ______________________________________                                         88      T.sub.1                                                                              B.sub.1  --CH.sub.2 --                                                                         yellow                                           89      T.sub.1                                                                              B.sub.2  "      "                                                90      T.sub.1                                                                              B.sub.4  "      "                                                91      T.sub.1                                                                              B.sub.5  "      "                                                92      T.sub.1                                                                              B.sub.6  "      "                                                93      T.sub.1                                                                              B.sub.7  "      "                                                94      T.sub.4                                                                              B.sub.3  "      orange                                           95      T.sub.4                                                                              B.sub.5  "      "                                                96      T.sub.4                                                                              B.sub.6  "      "                                                97      T.sub.4                                                                              B.sub.7  "      "                                                ______________________________________                                    

EXAMPLES 98 TO 106

Compounds of the formula ##STR72## in which the symbols T, X_(o) and R₂ are defined in Table III below, can be produced in accordance with the procedure described in Example 1.

                  TABLE III                                                        ______________________________________                                                             position        position of X.sub.o                        Ex.  T     R.sub.2  of R.sub.2                                                                            X.sub.o  on ring D and D.sub.1                      ______________________________________                                          98  T.sub.1                                                                              --OH     2      *--SO.sub.2 NH--                                                                        3,4'                                        99  T.sub.3                                                                              "        "      "        "                                          100  T.sub.4                                                                              "        "      "        "                                          101  T.sub.5                                                                              "        "      "        "                                          102  T.sub.1                                                                              "        "      "        4,4'                                       103  T.sub.4                                                                              "        "      "        "                                          104  T.sub.1                                                                              --NO.sub.2                                                                              3      --S--    "                                          105  T.sub.4                                                                              "        "      "        "                                          106  T.sub.4                                                                              --COOH   3      "        "                                          ______________________________________                                    

The compounds of Examples 104 and 105 give yellow dyeings, the compounds of Examples 98 to 103 give a brown shade and the compound of Example 106 gives orange dyeings. * The asterisked S atom is attached to phenyl ring D.

EXAMPLE 107

16.5 Parts of the compound of Example 100 are introduced into 200 parts of water with stirring and the mixture is heated to 60°. After addition of 5.2 parts copper sulphate pentahydrate and 4 parts sodium acetate, the resulting mixture i s heated to 80° and kept at this temperature for 7 hours. The resulting red solution is cooled to room temperature and, after addition of a solution of 45 parts sodium carbonate dissolved in 200 parts water, the precipitated reaction product is filtered and dried. The following dyestuff ##STR73## is obtained in powdered form. It dyes paper in a yellow-brown shade and the resulting dyeings have good light and wet-fastness properties.

EXAMPLE 108

By following the procedure of Example107 but using the disazo compound of Example 103 the corresponding 1:1 copper complex is obtained.

EXAMPLE 109

16.5 Parts of the compound of Example103 are introduced in 200 parts water with stirring and the mixture is heated to 60°. After addition of 5 parts potassium chromium (III) sulphate. 12H₂ O and 7 parts sodium acetate (cryst.), the mixture is heated to 93°-95°. The chromation is complete after 4 to 5 hours reaction at this temperature. The resulting mixture is cooled to room temperature after which 50 parts sodium carbonate dissolved in 250 parts water are added to the mixture. The precipitated reaction product is then filtered and dried. The dyestuff of the formula ##STR74## is obtained as a powder. When used in acid addition salt form, it dyes paper in a red-brown shade and the resulting dyeings have good light and wet fastness properties. The resulting waste water of the dyeings is practically colourless.

EXAMPLES 110 TO 114

By repeating the procedure of Example 109, but using the appropriate compounds, the following metal complexes are obtained.

                  TABLE III                                                        ______________________________________                                         Ex.     Metal Complex                                                                              Coordinates                                                ______________________________________                                         110     1:2     Cr      Compound of Example 100                                111     1:2     Co      Compound of Example 100                                112     1:2     Fe      Compound of Example 100                                113     1:2     Co      Compound of Example 103                                114     1:2     Fe      Compound of Example 103                                ______________________________________                                    

The compounds of Examples 110 to 114 dye paper in a brown shade,

EXAMPLES 115 AND 116

Compounds of the formula ##STR75## wherein X_(o) is --O--CH₂ --O-- or ##STR76## can be produced by a method analogous to that of Example 1 from appropriate reactants.

Application Example A

70 Parts of chemically bleached sulphite cellulose obtained from pinewood and 30 parts of chemically bleached sulphite cellulose obtained from birchwood are ground in 2000 parts of water in a Hollander. 0.2 Parts of the dyestuff of Example 1 in acid addition salt form are added into this pulp. Paper is produced from this pulp after mixing for 20 minutes. The absorbent paper which is obtained in this manner is dyed in a yellow tone and the waste water is practically colourless.

Application Example B

0.5 Parts of the dyestuff of Example 1 in acid addition salt form are added to 100 parts of chemically bleached sulphite cellulose which have been ground in a Hollander with 2000 parts of water. Sizing takes place after a thorough mixing for 15 minutes. The paper which is produced from this material has a yellow tone and has good wet fastness properties.

Application Example C

An absorbent web of unsized paper is drawn at a temperature of 40° to 50° through a dye solution having the following composition:

0.5 parts of the dyestuff of Example 1 (in acid addition salt form)

0.5 parts of starch

99.0 parts of water.

The dyebath excess is squeezed out through two rollers. The dried web of paper is dyed in a yellow tone and has good fastness properties.

Any of the dyes of Examples 2 to 116 may be used either in water-soluble salt form or in the form of a dye preparation, e.g. a granulate, in Application Examples A to C.

Application Example D

100 Parts of freshly tanned and neutralized chrome leather are agitated for 30 minutes in a vessel with a dyebath of 250 parts of water and 1 part of the dyestuff of Example 1 (in acid addition salt form) at 55° C. and are then treated in the same bath for 30 minutes with 2 parts of an anionic fatty liquor based on sulphonated train oil. The leather is then dried and prepared in the normal way, giving a leather evenly dyed in a yellow tone.

Other leathers can be similarly dyed by known methods.

Application Example E

2 Parts of the dyestuff of Example 1 (in acid addition salt form) are dissolved in 4000 parts of demineralised water at 40° C. 100 Parts of a prewetted cotton textile substrate are added and the bath is raised to boiling point over 30 minutes and held at the boil for 1 hour, topping up with water where necessary. After removing the dyed fabric from the bath,washing and drying, a yellow dyeing is obtained with good light fastness and wet fastness properties. The dyestuff exhausts practically totally and the waste water is practically colourless.

Any of the dyestuffs of Examples 2 to 116 may be used in place of that of Example 1 in Application Examples D and E.

Application Example F

15 kg waste paper, 25 kg bleached mechanical pulp and 10 kg unbleached sulphate cellulose are defibrated in a pulper into a 3% aqueous pulp slurry. This stock suspension is diluted to 2% in a dyeing chest. To this diluted suspension there are added first 5% by weight china clay and then 1,25 kg of a 5% acetic acid solution of the dyestuff of Example 1, the % being based on the dry weight of fibres. After 20 minutes, a 1% resin size dispersion (based on the weight of absolutely dry fibres) is added to the resulting pulp in the mixing chest. The homogeneous pulp slurry is then adjusted to pH 5 by addition of alum shortly before introduction into the paper machine.

A yellow 80 g/m² heavy bag paper is produced on the paper machine. The resulting dyed paper exhibits very good fastness properties to bleeding and good light fastness properties.

The resulting paper can almost completely be decolourized by hypochlorite. The residual dyestuff concentration in the waste liquor is substantially low.

Application Example G

Water is added to a dry pulp in a hollander consisting of 60% by weight of mechanical wood pulp and 40% by weight of unbleached sulphite cellulose and the slurry is beaten in order So obtain a dry content slightly exceeding 2.5% and having a beating degree of 40 SR. The slurry is then exactly adjusted to a high density dry content of 2.5%.

5 Parts of a 0.25% aqueous solution of the dyestuff of Example 1 are added to 200 parts of the above resulting slurry. The mixture is stirred for about 5 minutes and, after addition of 2% by weight resin size and then 4% by weight alum (based on the dry weight) is further stirred for a few minutes until homogeneous. The resulting pulp is diluted with about 500 parts water to a volume of 700 parts and then used for the production of sheets by suction on a sheet former. The resulting paper sheets are dyed in an intense yellow shade. The residual dyestuff concentration in the waste water from the sheet former has been measured photometrically (λmax.=448 nm) and is substantially low.

Any one of the dyestuffs of Examples 2 to 116 may be used in place of that of Example 1 in Application Examples F and G. The waste water exhibits a substantially low residual dyestuff concentration. 

What is claimed is:
 1. In a process for producing colored paper comprising the steps of incorporating a dye into paper pulp and producing paper from said paper pulp or the step of applying a dye to paper sheet, the improvement wherein said dye is a compound of the formula ##STR77## or an acid addition salt thereof, wherein each B is --A₁ --NR₇ R₈ or --A₁ --.sup.⊕ NR₇ R₈ R₉ A.sup.⊖, to two B's being identical,wherein each A₁ is linear or branched C₂₋₈ alkylene,each R₇ is C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by halo, hydroxy or cyano; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenyl ring of which is substituted by 1 to 3 substituents selected from halo, C₁₋₄ alkyl and C₁₋₄ alkoxy; C₅₋₆ cycloalkyl or C₅₋₆ cycloalkyl substituted by 1 to 3 C₁₋₄ alkyl groups, each R₈ is C₁₋₆ alkyl; C₂₋₆ alkyl monosubstituted by halo, hydroxy or cyano; phenyl(C₁₋₃ alkyl); phenyl(C₁₋₃ alkyl) the phenyl ring of which is substituted by 1 to 3 substituents selected from halo, C₁₋₄ alkyl and C₁₋₄ alkoxy; C₅₋₆ cycloalkyl or C₅₋₆ cycloalkyl substituted by 1 to 3 C₁₋₄ alkyl groups, and each R₉ is C₁₋₄ alkyl; phenyl(C₁₋₄ alkyl); 2-oxopropyl; carbamoylmethyl or 3-chloro-2-hydroxypropyl, or each --NR₇ R₈ is an unsubstituted saturated ring containing 1 to 3 hetero atoms, a saturated ring containing 1 to 3 hetero atoms and substituted by 1 to 3 C₁₋₄ alkyl groups or N'-aminoethylpiperazino, or each --.sup.⊕ NR₇ R₈ R₉ is pyridinium, pyridinium substituted by 1 to 3 C₁₋₄ alkyl groups, an unsubstituted saturated ring containing 1 to 3 hetero atoms, a saturated ring containing 1 to 3 hetero atoms and substituted by 1 to 3 C₁₋₄ alkyl groups or N--C₁₋₂ alkyl-N'-aminoethylpiperazinium, each R₁ is hydrogen, C₁₋₄ alkyl, C₅₋₆ cycloalkyl, phenyl, benzyl or phenylethyl, the two R₁ 's being identical, each R₂ is independently halo, nitro, carboxy, C₁₋₄ alkyl or C₁₋₄ alkoxy, each T is hydrogen or ##STR78## the two T's being identical, wherein each R₃ is independently hydrogen, C₁₋₄ alkyl, --N(R₅)₂ or --CON(R₅)₂, wherein each R₅ is independently hydrogen or C₁₋₄ alkyl, or --N(R₅)₂ is an unsubstituted saturated ring containing 1 to 3 hetero atoms or a saturated ring containing 1 to 3 hetero atoms and substituted by 1 to 3 C₁₋₄ alkyl groups, X_(o) is a direct bond, linear or branched C₁₋₄ alkylene, ##STR79## with the proviso that when at least one n is 1 or 2, X_(o) is a direct bond, linear or branched C₁₋₄ alkylene, ##STR80## wherein R₄₂ is halo, C₁₋₄ alkyl or C₁₋₄ alkoxy, each R₄₃ is independently linear or branched C₁₋₄ alkylene, ##STR81## each R₄₄ is independently hydrogen or C₁₋₄ alkyl, each R₄₅ is independently halo, hydroxy, methoxy, ethoxy, amino, 2-hydroxyethylamino, N,N-di-(2-hydroxyethyl)amino, --NH--(CH₂)_(m) --N(C₂ H₅)₂, N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino, piperidino or N'-aminoethylpiperazino, wherein m is 2 or 3, andeach g is independently 1, 2, 3 or 4, and each n is independently 0, 1 or 2, wherein each A.sup.⊖ is a non-chromophoric anion, andeach halo is fluoro, chloro, bromo or iodo.
 2. A process according to claim 1 wherein the dye is a compound of the formula ##STR82##
 3. A process according to claim 1 wherein the dye is an acid addition salt of a compound of the formula ##STR83##
 4. A process according to claim 1, or an acid addition salt thereof, wherein X is other than a direct bond, linear or branched C₁₋₄ alkylene, --CO--, --S--, --O--, --SO₂ --, ##STR84##
 5. A process according to claim 1 wherein the dye is a compound of the formula ##STR85## or an acid addition salt thereof, wherein each B' is --A₁ '--NR₇ 'R₈ ' or --A₁ '--.sup.⊕ NR₇ 'R₈ 'R₉ ' A.sup.⊖, the two B''s being identical,wherein each A₁ ' is --(CH₂)₂ --, --(CH₂)₃ --, --(CH₂)₄ --, ##STR86## each R₇ ' is C₁₋₆ alkyl, n--C₂₋₃ hydroxyalkyl, benzyl, 2-chloroethyl or 2-cyanoethyl,each R₈ ' is C₁₋₆ alkyl n-C₂₋₃ hydroxyalkyl, benzyl, 2-chloroethyl or 2-cyanoethyl, and each R₉ ' is methyl, ethyl, propyl or benzyl, or --NR₇ 'R₈ ' is pyrrolidino, piperidino, morpholino, piperazino, N'-methylpiperazino or N'-aminoethylpiperazino, or --.sup.⊕ NR₇ 'R₈ 'R₉ ' is pyridinium pyridinium substituted by 1 or 2 methyl groups or ##STR87## wherein Z₀ is a direct bond, ##STR88## each R₁ ' is methyl, ethyl, phenyl, benzyl or cyclohexyl, the two R₁ ' is being identical, each R₂ ' is independently hydrogen, methyl, ethyl, methoxy, ethoxy, chloro or bromo, and each T' is hydrogen or ##STR89## the two T''s being identical, wherein each R₃ ' is independently hydrogen, methyl, ethyl, amino or dimethylamino, and each R₅ ' is independently hydrogen, methyl or ethyl, or --N(R₅ ')₂ is pyrrolidino, piperidino, morpholino, piperazino or N'-methylpiperazino, wherein each R₁₀ is independently methyl or ethyl.
 6. A process according to claim 5 wherein the dye is a compound of the formula ##STR90## or an acid addition salt thereof, wherein each B" is --(CH₂)₂ --NR₇ "R₈ ", --(CH₂)₃ --NR₇ "R₈ ", --(CH₂)₂ --.sup.⊕ NR₇ "R₈ "R₉ " A.sup.⊖ or --(CH₂)₃ --.sup.⊕ NR₇ "R₈ "R₉ " A.sup.⊖, the two B"'s being identical,wherein each R₇ " is methyl or ethyl,each R₈ " is methyl or ethyl, and each R₉ " is methyl, ethyl or benzyl, or --NR₇ "R₈ " is piperidino, morpholino, piperazino, N'-methylpiperazino or N'-aminoethylpiperazino, or --.sup.⊕ NR₇ "R₈ "R₉ " is pyridinium, 2-picolinium, 3-picolinium, N-methylpiperidinium, N-methylmorpholinium, N-methylpiperazinium, N,N'-dimethylpiperazinium, N-methyl-N'-(2-aminoethyl)piperazinium or N,N',N'-trimethylpiperazinium A.sup.⊖, each R₁ " is methyl or phenyl, the two R₁ "'s being identical, each R_(2a) " is independently hydrogen, methyl, methoxy or chloro, each T" is hydrogen or ##STR91## the two T"'s being identical, wherein R₃ " is hydrogen or methyl, and X_(o) ', when each R_(2a) " is hydrogen, is a direct bond, ##STR92## and, when at least one R_(2a) " is other than hydrogen, is a direct bond, --CH₂ --, --(CH₂)₂ --, --(CH₂)₃ --, --CO--NH-- ##STR93## wherein R_(42a) is hydrogen, chloro, methyl or methoxy, R_(45a) is chloro, hydroxy, methoxy, ethoxy, amino, 2-hydroxyethylamino, N,N-di-(2-hydroxyethyl)amino, 3-(N,N-diethylamino)propylamino, N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino, piperidino or N'-aminoethylpiperazino, m is 2 or 3, each p is 1 or 2, and each t is 1, 2 or 3,with the proviso that X_(o) is attached to the 3- or 4-position of Ring D' and to the 3- or 4-position of Ring D₁ '.
 7. A process according to claim 6 wherein the dye is a compound of the formula ##STR94## or an acid addition salt thereof, wherein each is --(CH₂)₂ --K or --(CH₂)₃ --K, the two B"''s being identical,wherein each K is dimethylamino, diethylamino, morpholino, piperazino, N'-aminoethylpiperazino, trimethylammonium A.sup.⊖, diethylmethylammonium A.sup.⊖, pyridinium A.sup.⊖, 3-picolinium A.sup.⊖, N-methylmorpholinium A.sup.⊖, N-methyl-N'-aminoethylpiperazinium A.sup.⊖ or N,N',N'-trimethylpiperazinium 2A.sup.⊖, each T'" is hydrogen ##STR95## the two T'"'s being identical, and X_(o) " is a direct bond, --CH₂ --, --(CH₂)₂ --, --CO--NH--, ##STR96##
 8. A process according to claim 7 wherein the dye is a compound of the formula ##STR97##
 9. A process according to claim 7 wherein the dye is an acid addition salt of a compound of the formula ##STR98##
 10. A process according to claim 5 wherein the dye is a compound of the formula ##STR99## or an acid addition salt thereof, wherein each B"" is --(CH₂)₂ --K' or --(CH₂)₃ --K', the two B""'s being identical,wherein each K' is dimethylamino or diethylamino,each R₂ '" is independently hydrogen, methoxy or ethoxy, each T'" is hydrogen ##STR100## the two T'"'s being identical, and X_(o) ", when each R₂ '" is hydrogen, is a direct bond, ##STR101## and, when at least one R₂ '" is other than hydrogen, is ##STR102## wherein R_(42a) is hydrogen, chloro, methyl or methoxy, and R_(45a) is chloro, hydroxy, methoxy, ethoxy, amino, 2-hydroxyethylamino, N,N-di(2-hydroxyethyl)amino, 3-(N,N-diethylamino)propylamino, N-methyl-N-phenylamino, N-cyclohexyl-N-methylamino, piperidino or N'-aminoethylpiperazino.
 11. A process according to claim 10 wherein the dye is a compound of the formula ##STR103##
 12. A process according to claim 10 wherein the dye is an acid addition salt of a compound of the formula ##STR104##
 13. A process according to claim 10 wherein the dye is the compound of the formula ##STR105##
 14. A process according to claim 10 wherein the dye is an acid addition salt of the compound of the formula ##STR106##
 15. A process according to claim 10 wherein the dye is the compound of the formula ##STR107##
 16. A process according to claim 10 wherein the dye is an acid addition salt of the compound of the formula ##STR108##
 17. A process according to claim 10 wherein the dye is a compound of the formula ##STR109## wherein each A.sup.⊖ is a non-chromophoric anion.
 18. A process according to claim 10 wherein the dye is an acid addition salt of a compound of the formula ##STR110## wherein each A.sup.⊖ is a non-chromophoric anion.
 19. A process according to claim 17 wherein the dye is the compound of the formula ##STR111##
 20. A process according to claim 18 wherein the dye is an acid addition salt of the compound of the formula ##STR112## 